Textile printing composition



, compositions intended for textile decorating, 2,202,283, issued May 28, 1940), of which this is ening agents such as British gum, starch and the ble of producing permanent dyeings on the fabin order to get effective printing, and consider I v w discovered that this diflieulty can yerted dyestufl in the filmof thickener, partially tionof the insoluble dyestufl (e. g., urea formal- UNITED, STATES PATENT. OFFICE TEXTILE PRINTING COMPOSITION Norman S. Cassel, Ridgewood, N. J., assignor to Intel-chemical Corporation, New 'York, N. Y., a

corporation of Ohio No Drawing. Application May 27, 1940, Serial No. 327,495

3 Claims. (01. 8-62) This invention relates to the art of textile In my c'o-pending application, serial No. 215,- printing, and'is directed particularly to new 585, filed June 24, 1938 (now U. S. Patent No.

comprising emulsions of thickened aqueous dyea continuation in part, I have disclosed a means stuff dispersions in a continuous organic liquid '5 whereby these disadvantages may be overcome, phase. a and successful dyestuif printing can be done with The conventional method of textile printing inphotogravure and other relatively shallow envolves the application to a-textile fabric of a dye gravings, with the retention of the complete deor a dye component in water solution, by means tail of the photogravure cylinders, and the use of of an intaglio cylinder. In order to get the dye- 10 a minimum of dyestufi. As therein disclosed, this stuff solution thick enough to remain in the cells. means comprises the preparation of dyestuif of the printing cylinders, and to remain in place printing pastes by the emulsification of an aquewhen applied to the fabric, water-soluble thickous solution of a dye or a dye component capalike are used. More recently, wetting agents have rics with a water-immiscible bodying composition been added to the pastes to improve their print- (preferably a solution of a film-forming subing. properties. After printing, the dyes are set stance in a solvent), the dyestuff solution being by various means so that they become water-inin the discontinuous phase. The resultant emulsoluble, and the fabric is washed to remove the sion, of optimum consistency for'printing, is apwater-soluble thickeners. plied to a. fabric, as with a conventional intaglio Certain difficulties are encountered with these cylinder; the dyestuff is fixed on the fabric, and conventional dyestufi pastes. Since the fabrics the fabric is then dried,.with or without washing, printed are rather water-absorbent, prints made depending on the dyestufi employed. with water solutions, even when made viscous As the emulsion is applied to the cloth and with the water-soluble thickeners, tend to spread the emulsion breaks, the dyestuifv solution peneout slightly from the point of application, a trates into the yarns of the fabric. Since the waphenomenon known as flushing. As a-result, the ter phase and the bodying agent'are mutually relines in the engraving may become somewhat pellent, thenon-aqueous phase prevents undue blurred, and very fine lines close together may be spreadin o e aqueous p As a e entirely lost. When the viscosities of the pastes 0 stantially no'flushing occurs, and fine printing is are adjusted so'that no flushing occurs,- the pastes obtained, which preserves the fine lines of a phobecome too thick to separate cleanly from the togravure engraving even on materials which are engravings. A compromise must always be made, as diflicult to print as cotton fiannels.

so that eifective separation occurs without sub- While unusually sha p ight printsv are stantial flushing; and the cylinders must be sotained with these p With minimum Washing prepared as to print most easily. Fine photoaway of color, these pastes'have one disadvangravure engravings have, as 'a consequence, never t e- W eep e s. the q e inner been used with conventional textile printing Phase of the emulsion s O e en p o pastes, because their faithful reproduction of deh f i so t e colorin effect is iv n tail would not register on the fabric. Further- 40 deeper i the ri than ces ry, r l i more, the engravings used must be rather deep inreduced economy o y ably more paste is used than is really necessary be Overcome by ni e inner aqueous to produce most designs, phase of the emulsion with a water-dispersible Another disadvantage of conventional dyestufr thickener which imparts viscosity to the aquepastes is thata substantial quantity of dyestufi ous phase. If desired, the thickener in the aquemay be washed out with the thickeners. This is 0115 Phase y be a substance which s o e tdue partially to mechanical SUSPEDSiOM' co'ni l to a W r-in o dining the nn to incomplete conversion of. the dyestufi to the 0 dehyde resins, hydroxyethyl cellulose); in such insoluble form, due to the trapping of the solucases, the material may be used to impart a wabl dyestufi in i of th thickener film, and, in ter-insoluble finishto thefabric, or may supplesome cases, partially to actual dyeing of the ment the dyestufi with pigment. thickener. This may represent a serious loss of IheVe also discovered new compositions from dygatufl, which these thickened inner phase emulsions can leaches the thickener from the lacquer, to produce the-thickened inner phase emulsion.

The dyestufi may be added to the emulsion in any desired manner. One method of adding the dyestufi is to disperse it with the thickener in the lacquer, and permit the water to leach the dyestuff out together with the thickener. A second method is to add it in solution in the water used for making the emulsion and leaching the thickener. A third and perhaps the most flexible method is to make up a separate dyestuff emulsion to which no thickener has been added, and

to mix the thickened irmer phase emulsion with the dyestufi emulsion.

Typical examples of my invention are the following:

' EXAMPLE 1 Rapidogen dyestufl printing paste A dispersion of wheat starch in lacquer is prepared by 35 parts by weight dry wheat starch with a lacquer consisting of- 7 .parts byweight ethyl cel1ulose-standard ethoxy content-500 centipoise viscosity 11.6 parts by weight denatured alcohol 46.4 parts by weight toluene An emulsion isthen prepared by mixing 6.5

parts of the above novel starch dispersion with 0.2 parts 75% latex 22.6 parts Solvesso #2 (hydrogenated petroleum naphtha, boiling range 135-17? C.) To this mixture is added a solution of- 1.25 parts caustic soda, in

l 69.45 parts water (hot) The mixture is thoroughly stirred and passed I through a colloid mill. The result is an uncolored emulsion containing 0.15% rubber and 0.45% ethyl cellulose, based on emulsion weight in the continuous phase, and 2.28% starch in the aqueous phase. v

Dyestufi maybe added to this emulsion either by dispersing it in the original lacquer, or by. dissolving it in the water. It may also be added by merely mixing the above emulsion with the desiredamount of a .dyestufl emulsion, such as Y 15 .50 partswater A ratio of 2 or more thickened inner phase emulsion to 1 dyestuff emulsion is satisfactory. The print is developed by acid ageing in conventional fashion.

5 EXAMPLE 2 Stabilized azo dyestufi printing paste A dispersion is ma e With- J m 60 parts wheat starch, dispersed in a lacquer consisting of-- parts linseed oil modified glycerol phthalate resin (45% linseed oil, 55% glycerol phthalate) parts mineral spirits (petroleum naphtha I boiling range l50-200 C.) 4 parts water 1 part 40% formaldehyde The water aids in dispersing the starch, being absorbed by it.

A thickened emulsion can then be made from This is an acid stable emulsion, which can be used to make pastes with acid dyestuiif components such as diazo salts. Thus, the above 30 thickened emulsion can be used to mix with a dyestuff emulsion; or dyestuff can be dissolved in the boiling water used in the preparation of the thickened emulsion from the starch dispersion. Typical of the diazo compounds which can be used is Variamine Blue RT (Generej 'fDyestuffs Corp-Schultz Color Index supplementary #1-#1l4A). These pastes are printed on fabric impregnated with coupling .components 0 to yield ingrain colors.

' EXAMPLE-3 Alginate dispersion A satisfactory thickened emulsion can be prepared from the following dispersion, using the same proportions and procedure as in Example 1, to produce the emulsion and the finished printing paste:

12 parts sodlumalginate '1 parts 500 centipoise ethyl cellulose 10 parts ethanol 71 parts toluene v 1 EXAMPLE 4 Dyestufl starch dispersion The dyestufi and starch may be dis rse d together int'oIa water-immiscible lacquer, and this a may be then treated with water Thus I ake a dispersion of-' M an 1.50 parts wheat starch 4.00 parts dyestui! (for example, ilmtro-o anisidine diazotized and couplediwithf guanidine, mixed withthe necessary 'amount of theortho-anisidide of "beta? hydroxy-naphthoic'"acidto coupleiwith -the dia2o'=eompound after 'hydrolysisbf the'guanidine) i q l iatn i t e i+. 0.36 parts r5001 oe'ntipolse. ethyl cellulose 70-016 parts latexlt75.%) ;0;40 parts denatured. alcohol 1:60partatoluene' I :12'.40-.- pairtsplne'oil 1.08 parts Solvesso #2 An emulsion is then made with 21.0 parts Solvesso #2 8.0 parts water, and 59.0 parts of a boiling mixture of 4.25 parts 25% caustic soda. 54.75 parts water This is arepresentative stron'g printing paste which may be reduced as desired for shade. The dye is 'set in an acid ager.

emulsiiying both the dyestuff solution and the starch solution into a lacquer; thus- 19.70 parts of a aqueous wheat starch solution, and

53.30 parts of a dyestufi solution, prepared by dissolving 7.5 parts of the dyestuff of Example 4,

. in 8.0 parts NaOH 84.5 parts H2O are emulsified into a lacquer comprising- 0.55 parts 500 centipoise ethyl cellulose 0.24 parts 75% latex 0.60 parts denatured alcohol 2.55 parts toluene 21.86 parts Solvesso #2 1.20 parts pine oil This paste is printed on cloth, and passed through an acid ager as in Example 1.

Vat dyestuffs. are particularly diflicult to print from aqueous emulsions, since the oxidized dyestuffs are often very hydrophobe, and tend to flush into the organic phase.

By dispersing them in the hydrophile materials I use to thicken the inner phase, this tend: ency to flush into the organic phase is counteracted. A typical example of thisphase of my invention is the following:

' EXAMPLE 6 V Vat dyestufi paste 51.5 parts of a 20% aqueous vat dyestufi paste, such as Indanthrene Violet 2B (1924 Color Index 1104) 36.0 parts glycerol 12.5 parts dry starch are heated to 75 C. until the .mass starts to thicken, and then passed over a three-roll mill to smooth out the paste.

70.0 parts by weight of the parts is then dispersed in a lacquer phase consisting of-- 1.33 parts by weight 500 centipoise ethyl cellulose 133 parts by weight rubber latex (75%) 9.00 parts by weight pineoil 18.34 parts by weight Solvesso #2 The vat dyestuff is developed by reduction and oxidation in conventional manner.

EXAMPLE 7 Pigment I Amixed dyestufi pigment print can be obtained by using a water-soluble thickener which can be made watet-insoluble-e. g., urea resins, hydroxy ethyl cellulose, etc. Thus, in Exampl 5, the 15% aqueous starch solution can be replaced by the same amount of a solution comprising- 6.0 parts by weight hydroxy ethyl cellulose 3.3 parts by weight NaOH 7.5 parts by weight lamp black 83.2 parts by weight water 0n passing through the acid ager after printing, the dyestufi is set' and the hydroxy ethyl cellulose insolubilized. A brown print of fairly good wash fastness is obtained.

While I have shown only a few examples of my invention, it is obvious that examples may be multiplied indefinitely without departing from the scope thereof, which is defined in the claims.

It is obvious that other dyestufis of the types shown may be used, and that water-soluble dyestufi components of other types (direct dyestufls, mordant dyestufis, etc.) may be applied to-cloth by the methods and compositions described herein. Obviously, acid, alkali and other chemicals necessary to put the dyestufis in solution may be added. Care should, however, be taken that the continuous phase of the emulsion be not attacked by the particular aqueous system employed.

Any thickener which is auto dispersible in the aqueous inner phase (water or aqueous solutions of chemicals) may be used in the aqueous inner phase. Enough should be present. to substan- ./tially increase the viscosity of the water; a marked improvement is attained when the consistency of'the inner phase equals that of a aqueous solution of wheat starch. The effect is cumulative with increasing percentages of thickener, but the increase in surface efiect is counteracted by the loss of color with the thickener, so that I prefer not to exceed 5% of the total printing paste. Satisfactory thickeners include starch, dextrine, British gum, water-soluble cellulose, derivatives (e. g., methyl cellulose), al-

kali-soluble cellulose derivatives (e. g., hydroxy ethyl cellulose), alginates, water-soluble synthetic resins (urea-formaldehyde, sodium salts of polyacrylates,etc.).

With respect to the continuous outer phase, the dissolved substance chosen need'be 'only sufflciently film-forming to be capable of forming a continuous phase about the dyestufi solution. I have found that water-immiscible solutions in organic solvents of most water-insoluble mmforming organic compounds may be used successfully, and have successfully used'bodied oils, al-' kyd resins, hydrophobe urea-formaldehyde resins, cumarone-indene resins, natural resins such as damar and batu, rosin glycerol ester gums,

cellulose esters such as nitrocellulose and cellulose acetate, cellulose ethers such as benzyl and ethyl cellulose, rubber and rubber derivatives, synthetic rubber-like materials such as polychloroprene, polyisobutylene, and fatty acid soaps which promote water-in-oil'emulsification. Sub stantially any water-immiscible solvents may be used; water-miscible solvents should be present in no more than small percentages or the stability of the emulsions may be seriously impaired.

The amount of solute employed should be kept at a minimum consonant withL stability of the emulsion, and in general the continuous phase should likewise be kept at a minimum. I prefer to maintain the water-immiscible solute under about 5% of the total emulsion weight. The total of water-soluble thickener and water-insoluble film-forming solute used should preferably be'kept.z.under 10% of the total emulsion, and mostzi-preferablyis kept below 5%, as will be observed the examples.

In the specification and claims, the term dyestuff means a complete dye, or a component of a dye, and the term "undeveloped dyestuff means that the dye or dye component is in such iorm'that it lacks the color of the finished dye on the fabric. 4

Iclaim: v

1. A textile dyestufi decorating paste comprising an emulsion,.the outer phase of which comprises a water-unmiscible, solution of a waterdium thickened by the dispersion of an autodispersible thickener therethrough to a consistency at least equal to that of a /2% aqueous wheat starch dispersion, the quantity of autodispersible thickener being at least about as great as the quantity of water-insoluble film-forming substance, and not to exceed 5% of the paste.

2. A textile dyestuif decorating paste comprising an emulsion, the outer phase of which com- ,as the quantity of water-insoluble film-forming insoluble film-forming substance ina volatile organic solvent, and the inner phase of which comprises a solution of a dyestufi in an aqueous mesubstance, the ,auto-dispersible thickener and film-forming substance together comprising not to exceed 5% of the total paste.

3. The composition of claim 2, in which the dyestufi is undeveloped.

NORMAN S. CASSEL. 

